United States Patent
`
`Nishikawa et al.
`
`
`
`
`
`[19]
`
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`
`[11] Patent Number:
`
`
`[45] Date of Patent:
`
`
`
`
`
`5,969,055
`
`
`
`Oct. 19, 1999
`
`US005969055A
`
`
`
`[54] LIQUID CRYSTAL ALIGNMENT AGENT
`
`
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`
`
`[75]
`
`
`
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`
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`Inventors: Michinori Nishikawa, Suzuka; Kyouyu
`Yasuda, Tsu; Shigeo Kawamura,
`
`
`
`
`Yokkaichi; Tsukasa Toyoshima,
`
`
`
`Yokkaichi; Yasuo Matsuki, Yokkaichi;
`
`
`
`
`Kengo Wakabayashi, Yokohama, all of
`
`
`
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`Japan
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`
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`[73] Assignee: JSR Corporation, Tokyo, Japan
`
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`
`
`[21] Appl. No.:
`08/981,829
`
`
`
`
`PCT Filed:
`May 15, 1997
`
`
`
`
`
`[22]
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`
`
`[86]
`
`
`
`PCT No.:
`
`
`
`
`PCT/JP97/01635
`
`
`
`§ 371 Date:
`
`
`
`
`Jan. 15, 1998
`
`
`
`
`[87]
`
`
`
`[30]
`
`
`Jan. 15, 1998
`§ 102(e) Date:
`
`
`
`
`
`
`PCT Pub. No.: W097/43687
`
`
`
`
`PCT Pub. Date: Nov. 20, 1997
`
`
`
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`
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`Foreign Application Priority Data
`
`
`
`
`
`[JP]
`Japan .................................. .. 8—146840
`May 16, 1996
`
`
`
`
`Japan .................................. .. 8—352142
`Dec. 12, 1996
`[JP]
`
`
`
`
`Int. Cl.5 .......................... .. G02F 1/1337; G02F 1/13;
`
`
`
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`C09K 19/56
`
`
`........................ .. 525/419; 525/425; 525/428;
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`
`
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`
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`525/430; 252/299.4
`[58] Field of Search ................................... .. 525/419, 425,
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`525/428, 430, 252/299.4
`
`
`
`
`[51]
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`
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`[52] U.S. Cl.
`
`
`
`[56]
`
`
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`
`
`
`
`
`
`References Cited
`
`
`U.S. PATENT DOCUMENTS
`
`
`5,276,132
`.
`1/1994 Nishikawa et al.
`
`
`
`
`5,298,590
`3/1994 Isogai et al.
`.......................... .. 528/188
`
`
`
`
`
`5,478,682 12/1995 Nishikawa et al.
`.
`
`
`
`
`3/1997 Mizushima et al.
`.
`5,612,450
`
`
`
`
`12/1997 Nishikawa et al.
`.
`5,698,135
`
`
`
`
`5,700,860 12/1997 Nishikawa et al.
`.
`
`
`
`
`FOREIGN PATENT DOCUMENTS
`
`
`63—243917 10/1988
`
`64-4720
`1/1989
`
`64-6924
`1/1989
`
`1—295226
`11/1989
`
`
`
`
`
`
`
`Japan .
`
`Japan .
`
`Japan .
`
`Japan .
`
`
`Primary Examiner—Nathan M. Nutter
`
`
`
`Attorney, Agent, or Firm—Oblon, Spivak, McClelland,
`
`
`
`
`
`
`
`
`Maier & Neustadt, P.C.
`
`
`
`[57]
`
`
`
`ABSTRACT
`
`
`
`
`
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`
`
`
`
`
`A liquid crystal alignment agent containing at least two
`kinds of polymers selected from the group consisting of
`
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`polyamic acids and imidized polymers and having a struc-
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`
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`ture obtained by dehydration and ring closure of polyamic
`acid. In the at least two kinds of polymers contained in the
`
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`
`
`liquid crystal alignment agent, the polymer of higher imi-
`
`
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`dization degree has a smaller surface free energy. The liquid
`
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`crystal alignment agent gives a liquid crystal display device
`
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`having less stuck image and high pretilt angle.
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`10 Claims, No Drawings
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`Page 1 of 19
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`Tianma Exhibit 1009
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`Page 1 of 19
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`Tianma Exhibit 1009
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`

`
`5,969,055
`
`
`
`1
`
`LIQUID CRYSTAL ALIGNMENT AGENT
`
`
`
`
`
`This application claims the benefit under 35 USC 371 of
`
`
`
`
`
`
`
`prior PCT International Application No. PCT/JP 97/01635
`
`
`
`
`
`
`
`which has an international filing date of May 15, 1997.
`
`
`
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`
`
`
`TECHNICAL FIELD
`
`
`
`The present invention relates to a liquid crystal alignment
`
`
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`
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`agent. More specifically, the present invention relates to a
`
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`liquid crystal alignment agent which can give a liquid crystal
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`alignment film having good liquid crystal alignability and
`can provide a liquid crystal display device with a high pretilt
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`angle and excellent stuck image-free properties.
`
`BACKGROUND ART
`
`
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`There have heretofore been known TN type liquid crystal
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`display devices having a TN (twisted nematic) type liquid
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`crystal cell which comprises two substrates each having, on
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`the surface, a liquid crystal alignment film via a transparent
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`electroconductive film and a nematic liquid crystal layer
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`having a positive dielectric anisotropy, the nematic liquid
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`crystal layer being interposed between the two substrates so
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`as to form a sandwich structure, in which liquid crystal cell
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`the major axes of liquid crystal molecules are continuously
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`twisted by 90° in the direction extending from one of the
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`substrates to the other substrate. The alignment of liquid
`
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`crystal in the TN type liquid crystal devices is made gen-
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`erally by a liquid crystal alignment film imparted with an
`
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`alignability for liquid crystal molecules by a rubbing treat-
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`ment. As the material for the liquid crystal alignment film,
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`there are hitherto known resins such as polyimide,
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`polyamide, polyester and the like. Polyimides, in particular,
`
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`are used in many liquid crystal display devices because of
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`the excellency in heat resistance, compatibility with liquid
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`crystal, mechanical strengths, etc.
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`When a TN type liquid crystal display device is produced
`
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`using a liquid crystal alignment film formed of convention-
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`ally used polyimide or the like, however, the liquid crystal
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`display device has problems in that it gives defective display
`
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`due to its low pretilt angle or an image sticking is caused
`
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`
`owing to its a large residual voltage. Hence,
`it has been
`
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`
`
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`desired to develop a liquid crystal alignment agent capable
`
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`of giving a liquid crystal display device which has a liquid
`
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`crystal alignment film of good liquid crystal alignability and
`a high pretilt angle and is excellent in low image retention
`
`
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`
`
`
`properties.
`
`DISCLOSURE OF THE INVENTION
`
`
`
`
`The present invention has been completed in view of the
`
`
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`
`
`
`above situation. The first object of the present invention is to
`
`
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`provide a liquid crystal alignment agent capable of giving a
`
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`
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`liquid crystal alignment film superior in liquid crystal align-
`ability.
`
`The second object of the present invention is to provide a
`
`
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`
`
`liquid crystal alignment agent capable of providing a high
`
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`
`pretilt angle.
`The third object of the present invention is to provide a
`
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`liquid crystal alignment agent giving a liquid crystal align-
`ment film for a liquid crystal display device having excellent
`
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`image retention properties.
`The other objects and advantages of the present invention
`
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`will become apparent from the following description.
`
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`Page 2 of 19
`
`2
`
`The above-mentioned objects and advantages of the
`
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`
`present invention can be achieved by a liquid crystal align-
`
`
`
`
`
`
`
`ment agent containing at
`two kinds of polymers
`least
`
`
`
`
`
`
`
`
`
`selected from the group consisting of polyamic acids and
`
`
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`imidized polymers having a structure obtained by dehydra-
`
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`
`
`tion and ring closure of polyamic acid, wherein in the at least
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`two kinds of polymers contained in the liquid crystal align-
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`ment agent, the polymer of higher imidization degree has a
`
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`
`smaller surface free energy.
`
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`
`The liquid crystal alignment agent of the invention may
`
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`further contain an epoxy compound as an additive. In this
`
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`it
`is preferable that
`least
`two kinds of the
`the at
`case,
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`polymers have an average imidization degree of 5 to 40%.
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`The liquid crystal alignment agent containing an epoxy
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`compound possesses an effect of giving an excellent long-
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`term stability to the resulting liquid crystal display device.
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`The present invention is hereinafter described in detail.
`
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`Each polymer used in the liquid crystal alignment agent of
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`the present invention can be obtained by reacting at least one
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`tetracarboxylic acid dianhydride and at least one diamine
`
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`compound both mentioned below in an organic solvent to
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`synthesize a polyamic acid and, as necessary, subjecting the
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`polyamic acid to dehydration and ring closure.
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`[Tetracarboxylic acid dianhydride]
`As the tetracarboxylic acid dianhydride used in the syn-
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`thesis of the above polyamic acid, there can be mentioned,
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`for example, aliphatic or alicyclic tetracarboxylic acid dian-
`
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`hydrides such as butanetetracarboxylic acid dianhydride,
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`1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-
`
`
`
`dimethyl- 1,2,3,4-cyclobutanetetracarboxylic acid
`
`
`dianhydride,
`1,3-dimethyl-1,2,3,4-
`cyclobutanetetracarboxylic acid dianhydride, 1,3-dichloro-
`
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`
`
`1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,
`
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`4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid
`
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`dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid
`
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`dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid
`
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`
`dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic acid
`
`
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`dianhydride, 2,3,5-tricarboxycyclopentylacetic acid
`
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`
`dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid
`
`
`
`dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic acid
`
`
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`dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydro-2,5-
`
`
`dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,
`
`9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-
`
`furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-
`hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-
`
`
`naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-
`
`methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]
`
`furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-
`(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-
`
`
`dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-
`
`
`dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,
`
`9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-
`
`naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,
`8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,
`
`
`2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofural)-3-methyl-
`
`
`
`
`3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo
`
`
`
`[2,2,2]-octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride
`
`
`
`
`
`
`and compounds represented by the following formulas (I) to
`
`(II):
`
`
`
`
`
`
`
`10
`
`
`
`15
`
`
`
`20
`
`25
`
`
`
`30
`
`35
`
`
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`
`
`Page 2 of 19
`
`

`
`5,969,055
`
`
`
`(1)
`
`
`(11)
`
`
`
`o
`
`
`
`0
`
`
`
`0
`
`
`
`R1
`
`R2
`
`
`
`
`R2
`
`
`
`o
`
`
`
`0
`
`
`
`0
`
`
`
`O
`
`
`R4
`
`
`o
`
`
`
`R4
`
`
`0
`
`
`
`o
`
`
`
`R3
`
`
`O
`
`
`0
`
`
`
`(wherein R1 and R3 are each a bivalent organic group having
`
`
`
`
`
`
`
`an aromatic ring; R25 and R45 are hydrogen atoms or alkyl
`
`
`
`
`
`
`
`
`
`
`groups and each of two R25 and two R45 may be the same
`
`
`
`
`
`
`
`
`
`
`
`or different); and aromatic tetracarboxylic acid dianhydrides
`
`
`
`
`
`
`
`such a5 pyromellitic acid dianhydride, 3,3',4,4‘-
`
`
`
`
`
`
`
`
`
`
`benzophenonetetracarboxylic acid dianhydride, 3,3‘,4,4‘-
`
`
`
`
`biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-
`
`10
`
`
`
`15
`
`20
`
`25
`
`
`
`4
`
`
`
`
`
`naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-
`
`
`
`
`naphthalenetetracarboxylic acid dianhydride, 3,3',4,4‘-
`
`
`
`
`
`
`biphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4‘-
`
`
`
`dimethyldiphenylsilanetetracarboxylic acid dianhydride,
`
`
`
`3,3‘,4,4‘-tetraphenylsilanetetracarboXylic acid dianhydride,
`
`
`
`
`1,2,3,4-furantetracarboxylic acid dianhydride, 4,4‘-bis(3,4-
`
`
`
`
`
`dicarboxyphenoxy)-diphenyl sulfide dianhydride, 4,4 '-bis
`
`
`
`
`(3,4 -dicarboxyphenoxy)-diphenylsulfone dianhydride, 4,4‘-
`
`
`bis(3,4-dicarboxyphenoxy)-diphenylpropane dianhydride,
`3,3‘,4,4'-perfluoroisopropylidenediphthalic acid
`
`
`
`
`
`dianhydride, 3,3‘,4,4‘-biphenyltetra-carboxylic acid
`
`
`
`
`dianhydride, bis(phthalic acid)phenylphosphine oxide
`
`
`
`
`dianhydride, p-phenylene -bis(triphenylphthalic acid)
`
`
`
`dianhydride, m-phenylene-bis(triphenylphthalic acid)
`
`
`
`
`
`dianhydride, bis(triphenylphthalic acid) -4,4‘-diphenyl ether
`dianhydride , bis(triphenylphthalic acid)-4,4‘-
`
`
`
`
`
`
`
`diphenylmethane dianhydride, ethylene glycol-bis
`
`
`
`(anhydrotrimellitate), propylene glycol-bis
`
`
`(anhydrotrimellitate),
`1,4-butanediol-bis
`
`
`1,6-hexanediol-bis
`(anhydrotrimellitate),
`
`
`1 ,8-octanediol-bis(anhydro-
`(anhydrotrimellitate),
`
`trimellitate),2,2-bis(4-hydroXyphenyl)propane-bis
`
`
`
`
`
`(anhydrotrimellitate) and the compounds represented by the
`following formulas (1) to
`These compounds can be used
`
`
`
`
`
`
`
`singly or in combination of two or more kinds.
`
`
`
`
`
`
`Hsc
`
`
`
`H3C
`
`
`
`00C
`
`
`
`CO0
`
`
`
`
`
`
`TH3
`TH3
`CH CH CH
`
`
`(
`2)3'CH3
`
`
`
`
`
`0
`
`
`
`0
`
`
`
`O
`
`
`
`(1)
`
`
`
`(2)
`
`
`
`
`‘EH3
`(re
`CH CH CH=C
`
`
`(
`lCH3
`2)3
`
`
`
`
`
`
`
`H3C
`
`
`
`H3C
`
`
`
`COO
`
`
`
`H3‘:
`
`
`
`CH3
`
`
`
`OOC
`
`
`
`Page 3 of 19
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`0
`
`
`
`0
`
`
`
`O
`
`Page 3 of 19
`
`

`
`5,969,055
`
`
`
`-continued
`
`
`
`
`re
`(re
`CH(CH3)3CH
`
`CH3
`
`o
`
`o
`
`o
`
`(3)
`
`
`
`(4)
`
`TH3
`TH3
`CH(CH3)3CH
`
`CH3
`
`o
`
`
`
`C00
`
`
`
`0
`
`0
`
`o
`
`o
`
`0
`
`o
`
`0
`
`
`
`
`dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydro-2,5-
`
`
`dioxo-3-furanyl)-naphtho[2-c]furan-1,3-dione, 1,3,3a,4,5,
`
`9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioXo-3-
`
`
`
`
`45 furanyl)-naphtho[1,2-c]furan-1,3-dione, pyromellitic acid
`dianhydride and the compounds represented by the follow-
`
`
`
`
`
`
`
`
`
`ing formula
`
`50
`
`55
`
`
`
`60
`
`65
`
`
`
`o
`
`
`
`o
`
`
`
`o
`
`
`
`o
`
`
`
`o
`
`
`
`o
`
`
`
`(5)
`
`
`
`(6)
`
`
`
`o
`
`
`
`o
`
`
`
`o
`
`
`
`o
`
`
`
`0
`
`
`
`o
`
`
`
`CH3
`
`
`
`H3C
`
`
`
`Of the above compounds, the following compounds are
`
`
`
`
`
`
`
`preferred from the Viewpoint of achievement of good liquid
`
`
`
`
`
`
`
`
`
`crystal alignability:
`Butanetetracarboxylic acid dianhydride, 1,2,3,4-
`
`
`
`
`
`
`
`
`cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-
`1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,
`
`
`
`
`
`
`
`
`4-cyclopentanetetracarboxylic acid dianhydride, 2,3,5-
`
`
`
`tricarboxycyclopentylacetic acid dianhydride, 5-(2,5-
`dioxotetrahydrofural)-3-methyl-3-cycloheXene-1,2-
`
`
`
`
`dicarboxylic acid dianhydride, 1,3,3a, 4,5,9b-heXahydro-5-
`(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-
`
`
`dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-
`
`
`dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,
`
`9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioXo-3-
`
`
`furanyl)-naphtho[1,2-c]-furan-1,3-dione, bicyclo[2,2,2]-
`
`
`
`octo-7-ene-2,3,5,6-tetra-carboxylic acid dianhydride,
`acid dianhydride, 3,3‘,4,4‘-
`pyromellitic
`
`
`
`
`benzophenonetetracarboxylic acid dianhydride, 3,3‘,4,4‘-
`
`
`
`
`
`
`
`
`biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-
`naphthalenetetracarboxylic acid dianhydride,
`the
`
`
`
`
`
`
`
`
`
`
`compounds represented by the following formulas (5) to (7)
`out of the compounds of the formula (I), and the compounds
`
`
`
`
`
`
`
`
`
`represented by the following formula (8) out of the com-
`
`
`
`
`
`
`
`
`
`pounds of the formula (II). Particularly preferred are 1,2,3,
`
`
`
`
`
`
`
`
`
`
`
`
`4-cyclobutane-tetracarboxylic acid dianhydride, 1,3-
`dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid
`
`
`
`
`
`dianhydride, 2,3,5-tricarboxycyclopentylacetic acid
`
`
`
`
`
`Page 4 of 19
`
`Page 4 of 19
`
`

`
`5,969,055
`
`
`
`10
`
`
`
`20
`
`25
`
`
`
`30
`
`-continued
`
`
`
`O
`
`
`
`O
`
`
`
`O
`
`
`
`O
`
`
`
`
`O
`
`
`
`o
`
`
`
`O
`
`
`
`O
`
`
`
`(7)
`
`
`
`O
`
`
`
`
`
`(8)
`
`
`
`O
`
`
`
`
`
`
`
`[Diamine Compound]
`As the diamine compound used in the synthesis of the
`
`
`
`
`
`
`
`
`polyamic acid, there can be mentioned, for example,
`
`
`
`
`
`
`
`aromatic diamines such as p-phenylenediamine,
`
`
`
`
`
`
`
`m-phenylenediamine, 4,4‘-diaminodiphenylmethane,
`
`
`4,4‘-diaminodiphenylethane, 4,4‘-diaminodiphenyl
`
`
`
`sulfide, 4,4'-diaminodiphenylsulfone, 3,3‘-dimethyl-4,
`4'-diaminobiphenyl, 4,41-diaminobenzanilide, 4,4‘-
`
`
`
`
`
`
`
`diaminodiphenyl ether, 1,5 -diaminonaphthalene, 3,3-
`
`
`dimethyl-4,4‘-diaminobiphenyl, 5-amino- 1 -(4‘ -
`
`
`
`aminophenyl)- 1,3,3-trimethylindane, 6-amino-1-(4‘-
`
`
`aminophenyl)- 1 ,3,3 -trimethylindane, 3,4‘ -
`
`
`diaminodiphenyl ether, 3,3‘-diaminobenzophenone,
`
`
`3,4‘-diaminobenzophenone,
`4,4‘-
`
`
`diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)
`
`
`phenyl]propane, 2,2-bis[4-(4-aminophenoxy)-phenyl]
`
`
`hexafluoropropane, 2,2-bis(4-aminophenyl)
`
`
`hexafluoropropane, 2,2-bis[4-(4-amino-phenoxy)
`
`
`
`phenyl]sulfone, 1,4-bis(4-aminophenoXy)benzene, 1,3-
`
`
`bis(4-aminophenoXy)benzene,
`1 ,3-bis(3-
`
`
`aminophenoXy)benzene, 9,9-bis(4-aminophenyl)-10-
`
`
`
`hydroanthracene, 2,7-diamino-fluorene, 9,9-bis(4-
`
`
`aminophenyl)fluorene, 4,4‘-methylene-bis(2-
`chloroaniline), 2,2‘,5,5‘-tetrachloro-4,4‘-
`
`
`diaminobiphenyl, 2,2‘-dichloro-4,4‘-diamino-5,5‘-
`
`
`
`
`dimethoxybiphenyl, 3,3'-dimethoXy-4,4‘-
`
`
`diaminobiphenyl, 1,4,4'-(p-phenylene-isopropylidene)
`
`
`bisaniline, 4,4‘-(m-phenyleneisopropylidene)
`bisaniline,
`2,2‘-bis[4-(4-amino-2-
`
`
`
`trifluoromethylphenoxy)phenyl]-hexafluoropropane,
`
`
`4,4‘-diamino-2,2‘-bis(trifluoromethyl)biphenyl, 4,4‘-bis
`
`[(4-amino-2-trifluoromethyl)phenoXy]-
`octafluorobiphenyl and the like;
`
`
`
`
`aliphatic or alicyclic diamines such as 1,1-
`
`
`
`
`
`
`
`
`
`metaxylylenediamine, 1,3-propanediamine,
`
`
`tetramethylenediamine, pentamethylenediamine,
`
`
`hexamethylenediamine, heptamethylenediamine,
`
`
`
`octamethylenediamine, nonamethylenediamine, 4,4-
`
`
`diaminoheptamethylenediamine,
`1,4-
`
`
`isophoronediamine,
`diaminocyclohexane,
`
`
`tetrahydrodicyclopentadienylenediamine, heXahydro-
`
`
`4,7-methanoindanylenedimethylenediamine,
`tricyclo
`
`
`[6.2.1.02,7]-undecylenedimethyldiamine, 4,4‘-
`
`
`
`
`
`methylene bis-(cyclohexylamine) and the like;
`
`Page 5 of 19
`
`
`8
`diamines having, in the molecule, two primary amino
`
`
`
`
`
`
`
`
`groups and a nitrogen atom(s) other than the above
`
`
`
`
`
`
`
`
`primary amino groups, such as 2,3-diaminopyridine,
`
`
`
`
`
`
`
`
`2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-
`
`
`diaminopyridine, 5,6-diamino-2,3-dicyanopyrazine,
`
`
`5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-
`
`
`dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)
`
`
`piperazine, 2,4-diamino-6-isopropoXy-1,3,5-triazine,
`
`
`2,4-diamino-6-methoXy-1,3,5-triazine, 2,4-diamino-6-
`
`
`phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine,
`
`
`2,4-diamino-1,3,5-triazine, 4,6-diamino-2-Vinyl-s-
`
`
`
`triazine, 2,4-diamino-5-phenylthiazole, 2,6-
`
`
`
`diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-
`
`
`diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine
`
`
`
`lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-
`
`
`
`diaminopiperazine, 3,6-diaminoacridine, bis(4-
`
`
`
`
`aminophenyl)phenylamine,
`the compounds repre-
`sented by the following formulas (III) to (VI), and the
`
`
`
`
`
`
`
`
`
`like;
`
`
`(III)
`
`
`
`Vi?
`
`HZN
`
`NH2
`
`/
`
`\7
`
`
`
`
`
`
`
`
`(wherein R5 is a monovalent organic group having a
`nitrogen-containing ring structure selected from the group
`
`
`
`
`
`
`
`consisting of pyridine, pyrimidine, triazine, piperidine and
`
`
`
`
`
`
`
`piperazine; and X is a bivalent organic group)
`
`
`
`
`
`
`35
`
`
`
`(IV)
`
`
`
`40
`
`45
`
`
`
`50
`
`55
`
`
`
`60
`
`65
`
`
`
`(wherein R6 is a bivalent organic group having a nitrogen-
`
`
`
`
`
`
`containing ring structure selected from the group consisting
`
`
`
`
`
`
`
`
`of pyridine, pyrimidine, triazine, piperidine and piperazine;
`
`
`
`
`
`
`
`and Xs may be the same or different and are each a bivalent
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`organic group) mono-substituted phenylenediamines repre-
`
`
`
`
`
`sented by the following formula (V):
`
`L 8
`
`(V)
`
`flUV/J/
`
`HZN
`
`NH2
`
`(wherein R7 is a bivalent organic group selected from the
`
`
`
`
`
`
`
`O ,
`group consisting of
`COO ,
`OCO ,
`
`
`
`
`
`
`NHCO ,
`CONH and
`CO ; and R8 is a monova-
`
`
`
`
`lent organic group having a group selected from the group
`
`
`
`
`
`
`
`
`
`consisting of a steroid skeleton, a trifluoromethyl group and
`
`
`
`
`
`
`a fluoro group, or a C630 alkyl group);
`
`
`
`
`
`
`
`Page 5 of 19
`
`

`
`5,969,055
`
`
`diaminoorganosiloxanes represented by the following for-
`
`
`
`
`mula (VI):
`
`
`
`9
`
`(V1)
`
`
`
`
`
`10
`
`
`(wherein Rgs may be the same or different and are each a
`
`
`
`
`
`
`
`
`
`CH2 hydrocarbon group; p is an integer of 1 to 3; and q is
`
`
`
`
`
`
`
`
`an integer of 1 to 20); and
`
`
`
`
`
`
`
`
`T9
`T9
`
`H2N—§CH2§p—si—(.o—si—)T(—CH2—)p—NH2
`
`lg
`lg
`R
`R
`
`
`
`
`
`
`
`
`
`
`compounds represented by the following formulas (9) to
`
`
`
`
`
`
`
`(13). These diamine compounds can be used singly or
`in combination of two or more kinds.
`
`
`
`
`
`
`H3C
`
`
`
`H3C
`
`
`
`
`
`
`TH3
`TH3
`CH CH CH
`
`
`(
`2%
`
`
`CH3
`
`
`
`
`
`H3C
`
`
`
`H
`
`3C
`
`
`
`COO
`
`
`
`CH3
`CH3
`
`I
`I
`CH(CH3)3CH
`
`
`
`
`ICH3
`
`
`
`
`
`NH3
`
`
`
`CH3
`CH3
`
`I
`|
`CH(CH3)3CH
`
`
`
`
`
`
`
`
`
`
`
`(9)
`
`
`
`(10)
`
`
`
`(11)
`
`
`
`
`
`
`
`(12)
`
`
`
`
`
`
`
`
`
`NH3
`
`NH3
`
`Page 6 of 19
`
`Page 6 of 19
`
`

`
`5,969,055
`
`
`
`-continued
`
`
`
`(13)
`
`
`
`12
`
`
`
`11
`
`
`
`
`
`
`
`In the above formulas, y is an integer of 2 to 12 and Z is
`
`
`
`
`
`
`
`
`an integer of 1 to 5.
`
`
`
`
`Of
`the above compounds, preferred are
`
`
`
`
`
`
`
`
`p-phenylenediamine, 4,4‘-diaminodiphenylmethane, 4,4‘-
`
`
`
`
`diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-
`
`
`
`
`diaminofluorene, 4,4‘-diaminodiphenyl ether, 2,2-bis[4-(4-
`
`
`aminophenoxy)phenyl]-propane, 9,9-bis(4-aminophenyl)
`
`
`fluorene, 2,2-bis[4-(4-aminophenoXy)phenyl]
`
`
`hexafluoropropane, 2,2-bis(4-aminophenyl)
`
`
`hexafluoropropane, 4,4‘-(p-phenylenediisopropylidene)
`
`
`bisaniline, 4,4'-(m-phenylenediisopropylidene)bisaniline,
`1 ,4-cyclohexanediamine, 4,4‘-methylene bis
`
`
`
`
`
`
`
`10
`
`15
`
`
`
`20
`
`
`
`
`(cyclohexylamine), 1,4-bis(4-aminophenoXy)benzene, 4,4‘-
`
`
`
`
`bis(4-aminophenoXy)biphenyl, the compounds represented
`
`
`
`
`
`
`
`
`by the above formulas (9) to (13), 2,6-diaminopyridine,
`
`
`
`3,4-diaminopyridine, 2,4-diaminopyridine, 3,6-
`diaminoacridine, the compounds represented by the follow-
`
`
`
`
`
`
`
`
`
`
`
`
`
`ing formula (14) out of the compounds represented by the
`
`
`
`
`
`
`
`
`above formula (III),
`the compounds represented by the
`
`
`
`
`
`
`
`following formula (15) out of the compounds represented by
`
`
`
`
`
`
`
`
`the above formula (IV), and the compounds represented by
`the following formulas (16) to (21) out of the compounds
`
`
`
`
`
`
`
`
`
`
`
`
`represented by the above formula
`
`(14)
`
`
`
`(15)
`
`
`
`(1 6)
`
`
`(17)
`
`
`
`Coo—CH3CH3
`
`\ /N
`
`
`H3N
`
`NH3
`
`
`
`
`CH3
`<|:H CH CH/
`
`
`(
`2)3
`
`
`
`CH
`
`3
`CH3
`
`
`
`
`
`H3C
`
`
`
`H3C
`
`
`
`Coo
`
`
`
`
`
`H3N
`
`NH3
`
`
`
`CH
`
`H3C
`
`
`
`H3C
`
`
`
`Coo
`
`
`
`H3N
`
`
`
`NH3
`
`
`
`Page 7 of 19
`
`CH3
`
`3
`CH(CH3) CH/
`
`
`3 \CH3
`
`
`
`
`
`
`
`Page 7 of 19
`
`

`
`5,969,055
`
`
`
`
`
`-continued
`
`
`
`
`
`CH3
`CH3
`
`
`(‘H3
`CH CH CH=C
`(
`2)3
`
`
`
`H3C
`
`
`
`
`CH3
`\CH3
`
`
`
`
`
`CH3
`CH CH CH=C
`
`(
`2)3
`
`
`
`
`
`H3C
`
`H3C
`
`
`
`Coo
`
`
`
`HZN
`
`
`H3C
`
`
`NH2
`
`CH3
`
`
`
`
`H3C
`
`
`
`Coo
`
`
`
`H3N
`
`
`
`H3C
`
`CH3
`
`
`NH3
`
`
`(18)
`
`
`
`(19)
`
`
`
`(20)
`
`
`
`(21)
`
`
`
`
`
`Z CF
`/ 3
`\ /
`
`
`
`
`
`OOC
`
`: F
`/
`\ /
`
`
`
`OOC
`
`H3N NH3
`
`COO
`
`
`
`COO
`
`
`
`H3N NH3
`
`
`
`[Polyamic Acid]
`The tetracarboxylic acid dianhydride and the diamine
`
`
`
`
`
`
`
`compound used in the synthesis of the polyamic acid are
`
`
`
`
`
`
`
`
`
`used in such proportions that
`the acid anhydride group
`
`
`
`
`
`
`
`
`contained in the tetracarboxylic acid dianhydride is prefer-
`
`
`
`
`
`
`ably 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equiva-
`
`
`
`
`
`
`
`
`lents per 1 equivalent of the amino group contained in the
`
`
`
`
`
`
`
`
`diamine compound.
`
`
`The synthesis of the polyamic acid is conducted in an
`
`
`
`
`
`
`
`
`organic solvent usually at a reaction temperature of 0 to 150°
`
`
`
`
`
`
`C., preferably 0 to 100° C., for 1 to 48 hours. There is no
`
`
`
`
`
`
`
`
`
`
`particular restriction as to the kind of the organic solvent
`
`
`
`
`
`
`
`
`
`used as long as the solvent can dissolve the reaction products
`
`
`
`
`
`
`
`
`
`produced by the reaction. As the organic solvent, there can
`
`
`
`
`
`
`
`be mentioned, for example, aprotic polar solvents such as
`
`
`
`
`
`
`
`
`
`
`
`N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-
`
`
`
`
`dimethyl-formamide, dimethyl sulfoxide, y-butyrolactone,
`
`
`
`
`propylene carbonate, tetramethylurea, hexamethylphospho-
`
`50
`
`
`
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`60
`
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`65
`
`
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`ryl triamide and the like; and phenolic solvents such as
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`m-cresol, xylenol, phenol, halogenated phenol and the like.
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`The preferable amount of the organic solvent used is usually
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`such that the total amount of the tetracarboxylic acid dian-
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`hydride and the diamine compound accounts for 0.1 to 30%
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`by Weight of the total amount of the reaction solution.
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`The above organic solvent can be used in combination
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`with a poor solvent for the polyamic acid, such as alcohol,
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`ketone, ester, ether, halogenated hydrocarbon, hydrocarbon
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`or the like so long as the addition of the poor solvent does
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`not cause precipitation of the formed polyamic acid. Specific
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`examples of such a poor solvent include methyl alcohol,
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`ethyl alcohol,
`isopropyl alcohol, cyclohexanol, ethylene
`
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`glycol, propylene glycol, 1,4-butanediol, triethylene glycol,
`
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`acetone, methyl ethyl ketone, cyclohexanone, methyl
`acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl
`
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`malonate, diethyl ether, ethylene glycol methyl ether, eth-
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`ylene glycol ethyl ether, ethylene glycol monophenyl ether,
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`Page 8 of 19
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`Page 8 of 19
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`

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`5,969,055
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`15
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`ethylene glycol methylphenyl ether, ethylene glycol eth-
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`ylphenyl ether, diethylene glycol dimethyl ether, diethylene
`
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`glycol diethyl ether, diethylene glycol monomethyl ether,
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`diethylene glycol monoethyl ether, diethylene glycol
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`monomethyl ether acetate, diethylene glycol monoethyl
`ether acetate, ethylene glycol methyl ether acetate, ethylene
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`glycol ethyl ether acetate, 4-hydroxy-4-methyl-2-petanone,
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`2,4-pentane-dione, 2,5-hexanedione, ethyl
`
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`2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate,
`
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`ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate,
`
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`ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate,
`
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`methyl 3-methoxypropionate, ethyl 3-methoxypropionate,
`
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`ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate,
`
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`methyl pyruvate, ethyl pyruvate, hydroxymethyl pyruvate,
`methyl
`acetoacetate,
`ethyl
`acetoacetate,
`
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`methylmethoxybutanol, ethylmethoxybutanol,
`
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`methylethoxybutanol, ethylethoxybutanol, tetrahydrofuran,
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`tetrahydrofurfuryl alcohol, tetrahydro-3-furanmethanol, 1,3-
`
`
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`dioxolane, 1,3-dioxepan, 4-methyl-1,3-dioxolane,
`dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane,
`
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`
`trichloroethane, chlorobenzene, o-dichloroethane, hexane,
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`heptane, octane, benzene,
`toluene, xylene, and the like.
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`These solvents can be used singly or in combination of two
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`or more kinds.
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`By the above synthesis can be obtained a reaction solution
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`containing a polyamic acid dissolved therein. The reaction
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`solution is poured into a large amount of a poor solvent to
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`obtain a precipitate, and the resulting precipitate is dried
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`under reduced pressure, whereby a polyamic acid can be
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`obtained. Further,
`this polyamic acid can be purified by
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`again dissolving it in an organic solvent and then conducting
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`a step to precipitate it with the poor solvent once or several
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`times.
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`[Imidized Polymer]
`The imidized polymer constituting the liquid crystal
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`alignment agent of the present invention can be produced by
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`subjecting the polyamic acid to dehydration and ring clo-
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`sure. The dehydration and ring closure of the polyamic acid
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`is conducted by
`a method of heating the polyamic acid,
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`or (ii) a method of dissolving the polyamic acid in an organic
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`solvent, adding thereto a dehydrating agent and a catalyst for
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`dehydration and ring closure and, as necessary, followed by
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`heating.
`the
`of heating the polyamic acid,
`In the method
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`reaction temperature is usually 50 to 200° C., preferably 60
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`to 170° C. When the reaction temperature is lower than 50°
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`C.,
`the dehydration and ring closure reaction does not
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`proceed sufficiently. When the reaction temperature is higher
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`than 200° C., the imidized polymer obtained may have a
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`decreased molecular weight in some case.
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`Meanwhile, in the method (ii) of adding a dehydrating
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`agent and a catalyst for dehydration and ring closure to a
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`solution of the polyamic acid, there can be used, as the
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`dehydrating agent, for example, an acid anhydride such as
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`acetic anhydride, propionic anhydride, trifluoroacetic anhy-
`dride or the like. The amount of the dehydrating agent used
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`is preferably 0.01 to 20 moles per mole of the recurring unit
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`of the polyamic acid. As the catalyst for dehydration and
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`ring closure, there can be used, for example, a tertiary amine
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`such as pyridine, collidine, lutidine, triethylamine or the
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`like. However,
`the catalyst is not restricted thereto. The
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`amount of the catalyst for dehydration and ring closure is
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`preferably 0.01 to 10 moles per mole of the dehyrating agent
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`used. Incidentally, as the organic solvent used in the dehy-
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`dration and ring closure, there can be cited those specific
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`organic solvents mentioned in the synthesis of polyamic
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`acid. The reaction temperature of the dehydration and ring
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`10
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`15
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`20
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`25
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`30
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`35
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`40
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`45
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`50
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`55
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`60
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`65
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`Page 9 of 19
`
`
`16
`closure is usually 0 to 180° C., preferably 10 to 150° C. By
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`applying, to the thus-obtained reaction solution, the same
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`
`operation as employed in the purification of the polyamic
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`acid, the formed imidized polymer can be purified.
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`[Terminal-modified Polymer]
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`The polymer constituting the liquid crystal alignment
`agent of the present invention may be a terminal-modified
`
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`polymer having controlled molecular weight. By using a
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`terminal-modified polymer, the coating properties, etc. of
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`the liquid crystal alignment agent can be improved without
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`impairment of the effects of the present
`invention. The
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`
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`terminal-modified polymer can be synthesized by adding an
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`
`
`acid monoanhydride, a monoamine compound, a monoiso-
`
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`
`
`cyanate compound or the like to the reaction system, in the
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`
`
`synthesis of polyamic acid. As the acid monoanhydride,
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`there can be mentioned, for example, maleic anhydride,
`
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`
`
`phthalic anhydride,
`itaconic anhydride, n-decylsuccinic
`
`
`
`anhydride,
`anhydride,
`n-dodecylsuccinic
`
`
`
`
`n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhy-
`dride and the like. As the monoamine compound, there can
`
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`
`
`
`
`be mentioned, for example, aromatic monoamines such as
`
`
`
`
`
`
`
`aniline and the like; cycloalkylmonoamines such as cyclo-
`
`
`
`
`
`
`
`hexylamine and the like; alkylmono-amines such as
`
`
`
`
`
`
`
`
`
`
`
`n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine,
`
`
`
`n-octylamine, n-nonylamine, n-decylamine,
`
`
`
`n-undecylamine, n-dodecylamine, n-tridecylamine,
`
`
`
`n-tetradecylamine, n-pentadecylamine, n-hexadecylamine,
`
`
`
`
`n-heptadecylamine, n-octadecylamine, n-eicosylamine and
`and monoaminosilanes
`such as
`the
`like;
`
`
`
`
`
`
`3-aminopropyltrimethoxysilane ,
`
`
`3-aminopropyltriethoxysilane,
`2-aminopropyltrimethoxysilane ,
`
`
`
`2-aminopropyltriethoxysilane, N-ethoxycarbonyl-3-
`
`
`aminopropyltrimethoxy-silane, N-ethoxycarbonyl-3-
`
`
`aminopropyltriethoxysilane,
`N-benzyl-
`
`
`3-aminopropyltrimethoxysila